Pyridone compounds and the preparation of disulfonated pyridone compounds

ABSTRACT

There are described benzophenoneazo dyes of the formula ##STR1## where the ring A can be benzofused and a benzofused ring A can be overbridged, 
     m is 1 or 2, 
     K is the radical of a coupling component, 
     Y is hydrogen or arylazo, 
     one of the two radicals X 1  and X 2  is hydrogen and the other is hydroxysulfonyl, 
     R 1 , R 2  and R 3  are independently of the others hydrogen, halogen, C 1  -C 12  -alkyl, cyclohexyl, phenyl, 2-hydroxyethylsulfonyl or C 1  -C 4  -alkoxy or, when m is 1 and Y is hydrogen, one of these substituents can also be the radical of the formula ##STR2## where L 1  is a chemical bond or a bridge member, and 
     X 1 , X 2 , R 4 , K and the ring A are each as defined above, and 
     R 4  is hydrogen, halogen or C 1  -C 4  -alkoxy, with the proviso that there is at least one water-solubilizing group in the molecule, novel pyridone compounds, a process for preparing disulfonated pyridone compounds, and the use of the novel dyes for dyeing natural or synthetic substrates.

The present invention relates to a novel benzophenoneazo dye of the formula I ##STR3## where the ring A can be benzofused and a benzofused ring A can be bridged by C₂ H₄,

m is 1 or 2,

K is the radical of a 6-hydroxypyrid-2-one derivative which in ring position 3 is unsubstituted or substituted by carbamoyl, C₂ -C₅ -alkanoyl, hydroxysulfonylmethyl or hydroxysulfonyl, or is the radical of a coupling component of the phenylazopyridone, diaminopyridine, imidazolopyridine, aminopyrazole, hydroxypyrazole, aminothiazole, pyrimidine, indole, quinolone, aniline or aminonaphthalene series,

Y, when m is 1, is hydrogen or the radical --N═N--Q, where Q is the radical of a diazo or coupling component, or, when m is 2, is hydrogen,

X¹ and X² are identical or different and each is independently of the other hydrogen or hydroxysulfonyl,

R¹, R² and R³ are identical or different and each is independently of the others hydrogen, halogen, C₁ -C₁₂ -alkyl, cyclohexyl, phenyl, 2-hydroxyethylsulfonyl or C₁ -C₄ -alkoxy or, when m is 1 and Y is hydrogen, one of these substituents can also be the radical of the formula one of the two radicals X¹ and X² is hydrogen and the other hydroxysulfonyl,

R¹, R² and R³ are identical or different and each is independently of the others hydrogen, halogen, C₁ -C₁₂ -alkyl, cyclohexyl, phenyl, 2-hydroxyethylsulfonyl or C₁ -C₄ -alkoxy or, when m is 1 and Y is hydrogen, one of these substituents can also be the radical of the formula ##STR4## where L¹ is a chemical bond, C₁ -C₄ -alkylene, oxygen or a radical of the formula O--CH₂, O--CH₂ CH₂ --O, O--CH₂ CH₂ CH₂ --O or O--CH(CH₃)CH₂ --O, and X¹, X², R⁴, K and the ring A are each as defined above, and

R⁴ is hydrogen, halogen or C₁ -C₄ -alkoxy, to novel pyridone compounds, to a process for preparing disulfonated pyridone compounds, and to the use of the novel dyes for dyeing natural or synthetic substrates.

The novel benzophenoneazo dyes of the formula I are shown in the form of the free acid. However, their salts are of course also included.

The salts in question are metal or ammonium salts. Metal salts are in particular the lithium, sodium or potassium salts. Ammonium salts suitable for the purposes of the present invention are those salts which have either substituted or unsubstituted ammonium cations. Substituted ammonium cations are for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammonium cations or those cations which are derived from nitrogen-containing five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted products. Alkyl here is to be understood as meaning in general straight-chain or branched C₁ -C₂₀ -alkyl, which can be substituted by hydroxyl groups and/or interrupted by oxygen atoms.

EP-A-302,401 and the earlier patent application EP-A 413 229 disclose benzophenoneazo dyes which, however, have no water-solubilizing group in the molecule.

DE-A-2 223 622 describes a dye with 3-aminobenzophenone-4-sulfonic acid as diazo component and 1-methyl-6-hydroxy-3,4-trimethylenepyrid-2-one as coupling component.

Furthermore, DE-A-3 316 887 describes an azo dye whose coupling component is 1-hydroxysulfonylbenzyl-3-hydroxysulfonyl-4-methyl-6-hydroxypyrid-2-one.

EP-A-154 816 discloses azo dyes with 4-aminobenzophenone as diazo component and diaminopyridines as coupling component.

Finally, EP-A-126 324 describes a phenylazo dye with a sulfonated N-benzylpyridone as coupling component.

It is an object of the present invention to provide novel benzophenoneazo dyes which have at least one hydroxysulfonyl group in the molecule and advantageous application properties.

We have found that this object is achieved by the benzophenoneazo dyes of the formula I defined at the beginning.

Any alkyl or alkylene appearing in the above-mentioned formula I may be either straight-chain or branched.

If substituted phenyl groups appear in the formulae of the dyes of the invention, they generally have from 1 to 3 substituents. Suitable substituents are for example C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen and hydroxysulfonyl.

Coupling components KH of the pyridone or phenylazopyridone series conform for example to the formula IIc ##STR5## where W¹ is hydrogen or a radical of the formula ##STR6## where W² and W³ are identical or different and each is independently of the other hydrogen, methyl, ethyl or methoxy,

Z¹ is hydrogen, C₁ -C₄ -alkyl or phenyl,

Z² is hydrogen, carbamoyl, C₂ -C₅ -alkanoyl, hydroxysulfonylmethyl or hydroxysulfonyl, and

Z³ is hydrogen or C₁ -C₈ -alkyl which may be substituted by phenyl or hydroxysulfonylphenyl and may be interrupted by from 1 to 3 oxygen atoms in ether function.

Coupling components KH of the imidazolopyridine series conform for example to the formula IIe

Coupling components KH of the quinolone series conform for example to the formula IIh ##STR7## where Z¹³ is C₁ -C₄ -alkyl.

Coupling components KH of the pyrimidine series conform for example to the formula IIi or IIj ##STR8## where Z¹⁴ is C₁ -C₄ -alkyl or phenyl, and

Z¹, Z⁴, Z⁵ and Z⁶ are each as defined above.

Coupling components KH of the aniline series conform for example to the formula IIl ##STR9## where Z.sup. 15 is hydrogen or C₁ -C₆ -alkyl which may be unsubstituted or substituted by hydroxyl, C₁ -C₄ -alkoxy, cyano, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy, C₁ -C₄ -alkylaminocarbonyloxy, phenyl, hydroxysulfonylphenyl, C₁ -C₄ -alkoxycarbonyl or chlorine-, hydroxyl-, C₁ -C₄ -alkoxy- or phenoxy-substituted C₁ -C₄ -alkoxycarbonyl,

Z¹⁶ is hydrogen or C₁ -C₆ -alkyl which may be substituted by phenyl, hydroxysulfonylphenyl, C₁ -C₄ -alkoxycarbonyl or chlorine-, hydroxyl-, C₁ -C₄ -alkoxy- or phenoxy-substituted C₁ -C₄ -alkoxycarbonyl,

Z¹⁷ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or the radical --NH--CO--Q, where Q is C₁ -C₄ -alkyl, which may be C₁ -C₄ -alkoxy-, phenoxy-, cyano-, hydroxyl-, chlorine- or C₁ -C₄ -alkanoyloxy-substituted, or unsubstituted or C₁ -C₄ -alkoxy-substituted phenoxy, and

Z¹⁸ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

If Y is the radical --N═N--Q, Q is the radical of a diazo or coupling component.

Suitable diazo components Q¹ --NH₂ are derived for example from the aniline series. They conform for example to the formula III ##STR10## where U¹ is hydrogen, C₁ -C₄ -alkyl or hydroxysulfonyl and

U² is hydrogen, unsubstituted or sulfato-substituted C₁ -C₄ -alkyl, hydroxysulfonyl, phenylsulfonyloxy or 6-methyl - 7-hydroxysulfonylbenzothiazol-2-yl.

Suitable coupling components Q² --H are for example the abovementioned compounds of the formulae IIc, IIe, IIf, IIg, IIh, IIi, IIj, IIl or IIm, of which coupling components of the formula IIg are particularly noteworthy.

Radicals R¹, R², R³, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹², Z¹³, Z¹⁴, Z¹⁵, Z¹⁶, Z¹⁷,Z¹⁸, U¹ and U² are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

Radicals R¹, R², R³, Z³, Z⁴, Z⁵, Z⁶, Z¹¹, Z¹², Z¹⁵ and Z¹⁶ may each also be for example pentyl, isopentyl, neopentyl, tert-pentyl or hexyl.

Radicals R¹, R², R³, Z³, Z⁴, Z⁵, Z⁶, Z¹¹ and Z¹² may each also be for example heptyl, octyl, 2-ethylhexyl or isooctyl.

Radicals R¹, R², R³, Z⁴, Z⁵ and Z⁶ may each also be for example nonyl, isononyl, decyl, isodecyl, undecyl or dodecyl. (The above designations isooctyl, isononyl and isodecyl are trivial names derived from oxo process alcohols--cf. Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and also volume 11, pages 435 and 436.) are particularly noteworthy.

Radicals R¹, R², R³, Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁸, Z⁹, Z¹⁰, Z¹¹, Z¹², Z¹³, Z¹⁴, Z¹⁵, Z¹⁶, Z¹⁷, Z¹⁸, U¹ and U² are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

Radicals R¹, R², R³, Z³, Z⁴, Z⁵, Z⁶, Z¹¹, Z¹², Z¹⁵ and Z¹⁶ may each also be for example pentyl, isopentyl, neopentyl, tert-pentyl or hexyl.

Radicals R¹, R², R³, Z³, Z⁴, Z⁵, Z⁶, Z¹¹ and Z¹² may each also be for example heptyl, octyl, 2-ethylhexyl or isooctyl.

Radicals R¹, R², R³, Z⁴, Z⁵ and Z⁶ may each also be for example nonyl, isononyl, decyl, isodecyl, undecyl or dodecyl. (The above designations isooctyl, isononyl and isodecyl are trivial names derived from oxo process alcohols--cf. Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and also volume 11, pages 435 and 436.)

Radicals Z³, Z⁴, Z⁵, Z⁶, Z⁸, Z¹⁵ and Z¹⁶ may each also be for example benzyl, hydroxysulfonylbenzyl, 1- or 2-phenylethyl or 1- or 2-(hydroxysulfonylphenyl)ethyl.

Radicals Z⁸ and Z¹⁰ may each also be for example phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2,4-dichlorophenyl, 2-, 3- or 4-bromophenyl or 2-, 3- or 4-hydroxysulfonylphenyl.

Radicals Z³, Z⁴, Z⁵, Z⁶, Z¹¹ and Z¹² may each also be for example 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxa-heptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl or 3,6,9-trioxaundecyl.

Radicals Z⁴, Z⁵ and Z⁶ may each also be for example 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 5-hydroxy-3-oxapentyl, 6-hydroxy-4-oxahexyl, 8-hydroxy-4-oxaoctyl, 9-hydroxy-4,7-dioxanonyl, 2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybutyl, 6-phenoxy-4-oxahexyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 2-formyloxyethyl, 2-acetyloxyethyl, 2- or 3-formyloxypropyl, 2- or 3-acetyloxypropyl, 2- or 4-formyloxybutyl, 2- or 4-acetyloxybutyl, 5-formyloxy-3-oxapentyl, 5-acetyloxy- 3-oxapentyl, 6-formyloxy-4-oxaheptyl, 6-acetyloxy-4-oxyheptyl, 8-formyloxy-4-oxaoctyl, 8-acetyloxy-4-oxaoctyl, 9-formyloxy-4,7-dioxanonyl or 9-acetyloxy-4,7-dioxanonyl.

Z² is for example acetyl, propionyl, butyryl, isobutyryl or pentanoyl.

Z⁹ may also be for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or isobutoxycarbonyl.

R¹⁵ may also be for example 2-hydroxyethyl, 2- or 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-cyanoethyl, 2-formyloxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 4-acetyloxybutyl, 2-methoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl or 2-butylaminocarbonyloxyethyl.

Z¹⁵ and Z¹⁶ may each also be for example 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-isopropoxycarbonylethyl, 2-butoxycarbonylethyl, 2- isobutoxycarbonylethyl, 2-sec-butoxycarbonylethyl, 2-(2-chloroethoxycarbonyl)ethyl, 2-(2-hydroxyethoxycarbonyl)ethyl, 2-(2-methoxyethoxycarbonyl)ethyl, 2-(2-ethoxyethoxycarbonyl)ethyl, 2-(2-propoxyethoxycarbonyl)ethyl, 2-(2-isopropoxycarbonyl)ethyl, 2-(2-butoxyethoxycarbonyl)ethyl or 2-(2-phenoxyethoxycarbonyl)ethyl.

When Z¹⁷ is the radical NH--CO--Q, Q is for example methyl, ethyl, propyl, isopropyl, butyl, methoxymethyl, ethoxymethyl, 1- or 2-methoxyethyl, 1- or 2-ethoxyethyl, where m, K, Y, X¹, X², R¹, R², R³ and R⁴, are each as defined above.

Particular preference is given to benzophenoneazo dyes of the formula I where K is the radical of a 6-hydroxypyrid-2-one derivative which in ring position 3 is unsubstituted or substituted by carbamoyl, by C₂ -C₅ -alkanoyl, by hydroxysulfonylmethyl or by hydroxysulfonyl, the radical of a coupling component of the aminopyrazole or pyrimidine series, or a radical derived from the formula IIm.

Of note are benzophenoneazo dyes of the formula I where K is a radical of the formula IIc, IIf (Z⁷ =amino), IIi, IIj or IIm.

Also of note are benzophenoneazo dyes of the formula I where m is 1 and Y is hydrogen.

Also of note are benzophenoneazo dyes of the formula I where R¹, R² and R³ are each independently of the other hydrogen, chlorine, C₁ -C₄ -alkyl, in particular methyl or ethyl, methoxy or ethoxy.

Of particular importance are benzophenoneazo dyes which conform to the formula Ib, Ic or Id ##STR11## where one of the radicals X¹ and X² is hydrogen and the other is hydroxysulfonyl,

R¹ and R² are independently of each other chlorine, C₁ -C₄ -alkyl, in particular methyl or ethyl, methoxy or ethoxy,

R⁴ is hydrogen or methoxy, and

K is in each case as defined above.

Also of particular importance are benzophenoneazo dyes of the formula Ie or If ##STR12## where R¹, R² and R³ are each as defined above and

K¹ is 1-phenyl-3-methyl-5-aminopyrazol-4-yl, 2-amino-6-hydroxysulfonyl-8-hydroxynaphth-1-yl or a radical of the formula IIo ##STR13## where Z⁵ and Z⁶ are each as defined above.

Of industrial interest are benzophenoneazo dyes of the formula Ig ##STR14## where R¹ is hydrogen, C₁ -C₃ -alkyl or C₁ -C₄ -alkoxy, and

R² is C₁ -C₁₂ -alkyl, benzyl, phenylethyl or C₁ -C₄ -alkoxy in ring position 3 or 4, with the proviso that the total number of carbon atoms in the radicals R¹ and R² is from 4 to 12.

The novel aminobenzophenones of the formula I can be obtained in a conventional manner.

For example, an aminobenzophenone of the formula III ##STR15## where R¹, R², R³, R⁴, X¹, X² and the ring A are each as defined above, is diazotized in a conventional manner and coupled with a coupling component of the formula IV

    H--K--Y                                                    (IV)

where K and Y are each as defined above. ##STR16## where R¹, R², R³, R⁴, X¹, X² and the ring A are each as defined above, is diazotized in a conventional manner and coupled with a coupling component of the formula IV

    H--K--Y                                                    (IV)

where K and Y are each as defined above. When m in the formula I is 2 and K--Y is the radical of a bivalent coupling component of the formula IId, generally twice the amount is used of the diazonium salt obtainable from the aminobenzophenone III.

When Y in the formula I is the radical Q¹ --N═N--, the novel dyes can be obtained for example by first coupling the diazonium salt of the amine of the formula V

    Q.sup.1 --NH.sub.2                                         (V)

where Q¹ is as defined above, with the coupling component of formula IVa

    H--K--H                                                    (IVa)

where K is as defined above, and coupling the resulting monoazo dye of the formula VI

    H--K--N═N--Q.sup.1                                     (VI)

where Q¹ and K are each as defined above, with the diazonium salt of the aminobenzophenone III. However, it is also possible to carry out the coupling reactions in the reverse order.

It is further possible to replace the amine of the formula V by an aminobenzophenone of the formula III, in which case the disazo dye obtained contains two different or identical radicals of the diazo component of the formula III.

If the coupling component of the formula IVa is of the aniline or naphthalene series (formula IIl or IIm) and if it contains an unsubstituted amino group or a precursor thereof, the resulting monoazo dye of the formula VII ##STR17## where K¹ is the radical of a coupling component of the aniline or naphthalene series which has an amino group, and R¹, R², R³, R⁴, X¹, X² and the ring A are each as defined above, can also be diazotized again and coupled with a coupling component of the formula IVa. This again leads to disazo dyes.

The aminobenzophenones of the formula III are known compounds. They are described for example in the earlier European Patent Application No. 91112002.0.

The coupling components of the formula IV are likewise known products. They are described for example in D. R. Waring, G. Hallas, The Chemistry and Application of Dyes, Plenum Press, New York, 1990, or M. Okawara, T. Kitao, T. Hirashima, M. Matsuoka, Organic Colorants, Elsevier, Amsterdam, 1988, or in the references cited therein.

The present invention also provides novel pyridone compounds of the formula II ##STR18## where n is 1 or 2,

Z^(o) is hydrogen or C₁ -C₄ -alkyl, and

Z¹ is hydrogen, C₁ -C₄ -alkyl or phenyl.

Preference is given to pyridone compounds of the formula II where n is 1, Z¹ is C₁ -C₄ -alkyl, in particular methyl, and Z^(o) is hydrogen or methyl, in particular methyl.

Monosulfonic acids of a similar kind are known from DE-A-2,117,753.

The pyridone compounds II are highly suitable for use as coupling components for preparing azo dyes.

They can be obtained by reacting for example a hydroxypyridone of the formula VIII ##STR19## where n, Z^(o) and Z¹ are each as defined above, in a baking process or with concentrated sulfuric acid in a two-stage reaction in a one-got process in the presence or absence of oleum. In general, the first stage is carried out at from 30° to 70° C. and the second at from 120° to 150° C.

It has also been found that the preparation of the pyridone compounds of the formula IIa ##STR20## where a is 0, 1 or 2,

Z^(o) is hydrogen or C₁ -C₄ -alkyl and

Z¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, by reaction of pyridones of the formula IIb ##STR21## where W⁴ is cyano or acetyl and a, Z^(o) and Z¹ are each as defined above, with oleum is particularly successful on using oleum which contains from 1 to 2 mol of free sulfur trioxide and carrying out the reaction in a first stage at from 0° to 75° C. for from 1 to 5 hours and then in a second stage at from 80° to 135° C. for from 2 to 11 hours.

In this process, the sulfonic acid group goes into the phenyl ring in the first stage and into the pyridine ring in the second stage.

The reaction mixture is worked up in a conventional manner, for example by stirring out onto ice-water and subsequent neutralization, for example with sodium hydroxide solution.

The oleum used is advantageously a product which contains from 1 to 2 mol, preferably from 1 to 1.5 mol, of free sulfur trioxide.

The molar ratio of oleum:pyridone IIb is in general from 0.5:1 to 0.55:1, preferably from about 0.51:1.

It is also possible to use more oleum or oleum having a higher sulfur trioxide content, but this does not yield any further benefits. On the contrary, distinctly more ice-water and sodium hydroxide solution is required in the subsequent working up of the reaction mixture.

The novel benzophenoneazo dyes of the formula I are advantageously suitable for dyeing natural or synthetic substrates, for example wool, leather or polyamide. The dyes obtained have good general use fastness properties.

They are also suitable for the ink jet process.

The following Examples further illustrate the invention:

EXAMPLE 1

21.2 g of the diazo component of the formula ##STR22## were suspended with 60 ml of concentrated hydrochloric acid, 60 ml of glacial acetic acid and 0.2 g of an acidic wetting agent. The mixture was then cooled down to 0° C., and 31 ml of 23% strength by weight aqueous sodium nitrite solution were added at from 0° to 6° C. Presently a clear diazonium salt solution was obtained, which was subsequently stirred at from 0° to 6° C. for 2 hours. Excess nitrous acid was then destroyed with sulfamic acid. Then this mixture was mixed with 35.6 g of the coupling component of the formula ##STR23## which had beforehand been dissolved in 250 ml of water with 26 g of 50% strength by weight sodium hydroxide solution and cooled down to 0° C.

The coupling mixture was buffered at from 0° to 6° C. with sodium hydroxide solution at a pH of 3.5-4. The resulting dye of the formula ##STR24## was precipitated with sodium chloride, filtered off with suction, dried and ground. 120 g were obtained of a yellow powder having a dye content of 50% by weight.

The absorption maximum of a dye solution in a mixture of 1 g of glacial acetic acid and 9 g of N,N-dimethylformamide is 428 nm.

The dye produces dyeings on leather, nylon and wool in a bright yellow shade of good and wet and light fastness.

EXAMPLE 2

Example 1 was repeated, except that the coupling component was replaced by 35.7 g of the coupling component of the formula ##STR25## affording 59.5 g of the dye of the formula ##STR26## as a 50% strength by weight yellow powder whose absorption maximum in a solution of 9:1 g/g N,N-dimethylformamide/glacial acetic acid is 429 nm.

The dye gives deep bright yellow dyeings on wool and nylon having good fastness properties.

EXAMPLE 3

Example 1 was repeated, except that the coupling component was replaced by 20.5 g of the coupling component of the formula ##STR27## affording 42 g of the dye of the formula ##STR28## as a 90% strength by weight powder.

The dye produces bright yellow dyeings on nylon, wool and leather of good light fastness.

The ink jet process gives prints having good general use fastness properties.

The absorption maximum in water is 420 nm.

EXAMPLE 7

30.7 g of the diazo component 4-amino-4'-methoxybenzophenone-3'-sulfonic acid were diazotized as described in Example 6. The resulting suspension of the diazonium salt was admixed with 17.3 g of 1-phenyl-3-methyl-5-aminopyrazole, dissolved in 150 ml of water with 9 ml of concentrated hydrochloric acid. The pH of the reaction mixture was then gradually raised to 2.6-3.5 and subsequently stirred at pH 3-3.5 for 2 hours. The dye of the formula ##STR29## was salted out with sodium chloride and isolated, dried and ground in a conventional manner. This gave 51.2 g of the dye in the form of a 75% strength by weight yellow powder.

The dye has high affinity for nylon and wool and levels out differences in material in particular in the case of nylon. Its migration and light fastness properties on nylon are good. Nylon and wool are dyed a greenish yellow.

EXAMPLE 8

29.1 g of 4-amino-4'-methylbenzophenone-3'-sulfonic acid were diazotized as described in Example 6. After excess nitrous acid had been destroyed, the suspension of the diazonium salt was combined with a freshly prepared fine suspension of 31.9 g of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid which was acidified with hydrochloric acid to pH 0.5-0. The reaction mixture was left to stir overnight at 5°-10° C., producing a red dye of the formula ##STR30## λ_(max) (water): 601 nm

The dye was precipitated in full with sodium chloride and isolated in a conventional manner. The product thus isolated was dissolved with sodium hydroxide solution in 1000 ml of water at pH 6-9. The solution was then admixed with 0.1 mol of diazotized 4-amino-2',5'-dimethylbenzophenone, and the pH of the reaction mixture was maintained at >6-8. The resulting dye of the formula ##STR31## was precipitated with sodium chloride at pH 6-8 in the form of the trisodium salt and isolated in a conventional manner. This gave 120 g of a black powder which dyes leather, nylon and wool in a navy shade. The dye still contains about 24 g of sodium chloride.

The absorption maximum of the dye in water is 604 nm.

The same method was used to obtain the dyes listed below.

                                      TABLE 1                                      __________________________________________________________________________      ##STR32##                                                                     __________________________________________________________________________     Example                                                    λ.sub.ma                                                                x                   No.  K                    E           G            Hue     [nm]                __________________________________________________________________________      9                                                                                   ##STR33##           CONH.sub.2  CH.sub.2     bright yellow               10                                                                                   ##STR34##           COCH.sub.3  CH.sub.2     bright yellow               11                                                                                   ##STR35##           COCH.sub.3                                                                                  ##STR36##   bright yellow               12                                                                                   ##STR37##           COCH.sub.3  CH.sub.2 CH.sub.2 CH.sub.2                                                                  bright yellow               13                                                                                   ##STR38##           CONH.sub.2                                                                                  ##STR39##   bright yellow               14                                                                                   ##STR40##                                                                                           ##STR41##  C.sub.2 H.sub.5                                                                             yellow                      15                                                                                   ##STR42##           CH.sub.3                                                                                    ##STR43##   greenish yellow             16                                                                                   ##STR44##           H                                                                                           ##STR45##   greenish yellow             17                                                                                   ##STR46##           --          --           yellowish                   18                                                                                   ##STR47##           --          --           red     509 (in                                                                        water)              19                                                                                   ##STR48##           --          --           yellow                      __________________________________________________________________________     Example                                                                        No.  K             R.sup.1                                                                           R.sup.2                                                                              R.sup.3                                                                           G.sup.1      G.sup.2      Hue                   __________________________________________________________________________     20                                                                                   ##STR49##    H  CH.sub.3                                                                             H                                                                                  ##STR50##   C.sub.4 H.sub.9 (n)                                                                         yellow                21                                                                                   ##STR51##    CH.sub.3                                                                          CH.sub.3                                                                             H                                                                                  ##STR52##   C.sub.4 H.sub.9 (n)                                                                         yellow                22                                                                                   ##STR53##    CH.sub.3                                                                          H     CH.sub.3                                                                           ##STR54##   C.sub.4 H.sub.9 (n)                                                                         yellow                23                                                                                   ##STR55##    H  CH.sub.3                                                                             H  H                                                                                            ##STR56##   yellow                24                                                                                   ##STR57##    CH.sub.3                                                                          CH.sub.3                                                                             H  H                                                                                            ##STR58##   yellow                25                                                                                   ##STR59##    CH.sub.3                                                                          CH.sub.3                                                                             H  CH.sub.3                                                                                     ##STR60##   yellow                26                                                                                   ##STR61##    H  Cl    H  CH.sub.3     C.sub.6 H.sub.5                                                                             yellow                27                                                                                   ##STR62##    H  OCH.sub.3                                                                            H  OCH.sub.3    OCH.sub.3    orange                28                                                                                   ##STR63##    H  OCH.sub.3                                                                            H  OCH.sub.3    OCH.sub.3    orange                29                                                                                   ##STR64##    H  OCH.sub.3                                                                            H  CH.sub.3     CH.sub.3     orange                __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR65##                                                                     Example                                                                        No.     R.sup.1                                                                            R.sup.2                                                                               R.sup.3                                                                           X.sup.1                                                                               R.sup.5                                                                            R.sup.6                                                                               R.sup.7                                                                            R.sup.8                            __________________________________________________________________________     30      H   CH.sub.3                                                                              CH.sub.3                                                                          H      SO.sub.3 H                                                                         H      OCH.sub.3                                                                          H                                  31      CH.sub.3                                                                           CH.sub.3                                                                              H  H      SO.sub.3 H                                                                         H      OCH.sub.3                                                                          H                                  32      H   CH.sub.3                                                                              CH.sub.3                                                                          H      SO.sub.3 H                                                                         H      CH.sub.3                                                                           H                                  33      H   CH.sub.3                                                                              H  H      SO.sub.3 H                                                                         H      CH.sub.3                                                                           H                                  34      H   CH.sub.3                                                                              CH.sub.3                                                                          H      H   H      OCH.sub.3                                                                          SO.sub.3 H                         35      CH.sub.3                                                                           CH.sub.3                                                                              H  H      H   H      OCH.sub.3                                                                          SO.sub.3 H                         36      H   CH.sub.3                                                                              CH.sub.3                                                                          H      H   H      CH.sub.3                                                                           SO.sub.3 H                         37      H   CH.sub.3                                                                              H  H      H   H      CH.sub.3                                                                           SO.sub.3 H                         38      OCH.sub.3                                                                          H      CH.sub.3                                                                          H      H   CH.sub.3                                                                              CH.sub.3                                                                           SO.sub.3 H                         39      H   CH.sub.3                                                                              H  SO.sub.3 H                                                                            H   OCH.sub.3                                                                             CH.sub.3                                                                           H                                  40      H   OCH.sub.3                                                                             H  SO.sub.3 H                                                                            H   H      OCH.sub.3                                                                          H                                  41      H   C.sub.2 H.sub.5                                                                       H  H      SO.sub.3 H                                                                         H      C.sub.2 H.sub.5                                                                    H                                  42      H   C.sub.2 H.sub.5                                                                       H  H      H   H      C.sub.2 H.sub.5                                                                    SO.sub.3 H                         43      CH.sub.3                                                                           CH.sub.3                                                                              H  H      H   H      CH.sub.3                                                                           SO.sub.3 H                         44      H   Cl     H  H      H   H      CH.sub.3                                                                           SO.sub.3 H                         45      H   C.sub.2 H.sub.5                                                                       H  H      H   H      CH.sub.3                                                                           SO.sub.3 H                         __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR66##                                                                     Example                                                                        No.  R.sup.1                                                                           R.sup.2                                                                            R.sup.3                                                                            X.sup.1                                                                            X.sup.2                                                                            K                     Hue                              __________________________________________________________________________     46   H  CH.sub.3                                                                           H   SO.sub.3 H                                                                         H                                                                                   ##STR67##            orange                           47   H  CH.sub.3                                                                           CH.sub.3                                                                           SO.sub.3 H                                                                         H                                                                                   ##STR68##            orange                           48   H  CH.sub.3                                                                           CH.sub.3                                                                           H   SO.sub.3 H                                                                          ##STR69##            orange                           49   CH.sub.3                                                                          CH.sub. 3                                                                          H   SO.sub.3 H                                                                         H                                                                                   ##STR70##            orange                           50   H  OCH.sub.3                                                                          H   SO.sub.3 H                                                                         H                                                                                   ##STR71##            orange                           51   H  C.sub.2 H.sub.5                                                                    H   SO.sub.3 H                                                                         H                                                                                   ##STR72##            orange                           52   H  Cl  H   SO.sub.3 H                                                                         H                                                                                   ##STR73##            orange                           53   H  C.sub.2 H.sub.5                                                                    H   SO.sub.3 H                                                                         H                                                                                   ##STR74##            red                              54   H  CH.sub.3                                                                           H   SO.sub.3 H                                                                         H                                                                                   ##STR75##            red                              55   H  OCH.sub.3                                                                          H   SO.sub.3 H                                                                         H                                                                                   ##STR76##            red                              56   H  OCH.sub.3                                                                          SO.sub.3 H                                                                         H   H                                                                                   ##STR77##            red                              57   H  C.sub.2 H.sub.5                                                                    SO.sub.3 H                                                                         H   H                                                                                   ##STR78##            red                              58   H  CH.sub.3                                                                           SO.sub.3 H                                                                         SO.sub.3 H                                                                         H                                                                                   ##STR79##            yellow                           __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR80##                                                                     Example                                                                        No.  G.sup.1             G.sup.2            Hue                                __________________________________________________________________________     59                                                                                   ##STR81##                                                                                          ##STR82##         blue                               60                                                                                   ##STR83##                                                                                          ##STR84##         blue                               61                                                                                   ##STR85##                                                                                          ##STR86##         blue                               62                                                                                   ##STR87##                                                                                          ##STR88##         blue                               63                                                                                   ##STR89##                                                                                          ##STR90##         bluish black                       64                                                                                   ##STR91##                                                                                          ##STR92##         bluish black                       __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR93##                                                                     Example                                                                        No.  K                       X.sup.1                                                                            R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                              X.sup.2                                                                            Hue or λ.sub.max                                                        [nm]                          __________________________________________________________________________     65 66 67 68                                                                          ##STR94##              H H H SO.sub.3 H                                                                   H H H H                                                                           CH.sub.3 H H H                                                                    OCH.sub.3 OCH.sub.3 OCH.sub.3                                                  OCH.sub.3                                                                            SO.sub.3 H SO.sub.3 H                                                          SO.sub.3 H H                                                                       yellow yellow  yellow                                                          yellow                        69 70 71                                                                             ##STR95##              SO.sub.3 H SO.sub.3 H SO.sub.3 H                                                   H H CH.sub.3                                                                      H H H                                                                             OCH.sub.3 OCH.sub.3 H                                                                H H CH.sub.3                                                                       greenish yellow greenish                                                       yellow greenish yellow        72 73 74                                                                             ##STR96##              SO.sub.3 H H H                                                                     H CH.sub.3 H                                                                      H H H                                                                             CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                    H SO.sub.3 H SO.sub.3                                                              greenish yellow greenish                                                       yellow greenish yellow        75 76 77 78 79                                                                       ##STR97##              H SO.sub.3 H SO.sub.3 H SO.sub.3 H H                                               H H H H H                                                                         H H H H H                                                                         CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5                                             H(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                    H H H H SO.sub.3 H                                                                 greenish yellow greenish                                                       yellow greenish yellow                                                         greenish yellow greenish                                                       yellow                        80 81 82                                                                             ##STR98##              SO.sub.3 H SO.sub.3 H SO.sub.3 H                                                   H H H                                                                             CH.sub.3 H H                                                                      CH.sub.3 C.sub.2 H.sub.5 CH(CH.sub.                                            3).sub.2                                                                             H H H                                                                              yellowish red yellowish                                                        red yellowish red             83 84 85 86                                                                          ##STR99##              SO.sub.3 H SO.sub.3 H SO.sub.3 H SO.sub.3                                          H H H CH.sub.3                                                                    H CH.sub.3 H H                                                                    C.sub.3 H.sub.7 (i) CH.sub.3                                                   C.sub.2 H.sub.5 CH.sub.3                                                             H H H H                                                                            orange orange orange                                                           orange                        87 88                                                                                ##STR100##             SO.sub.3 H SO.sub.3 H                                                              H H                                                                               H CH.sub.3                                                                        C.sub.3 H.sub.7 (i)                                                                  H Hsub.3                                                                           403 404                       89 90                                                                                ##STR101##             SO.sub.3 H SO.sub.3 H                                                              H CH.sub.3                                                                        H H                                                                               C.sub.2 H.sub.5 CH.sub.3                                                             H H orange orange                 91 92 93                                                                             ##STR102##             SO.sub.3 H SO.sub.3 H SO.sub.3 H                                                   H CH.sub.3 H                                                                      H H H                                                                             CH.sub.3 CH.sub.3 C.sub.2 H.sub.5                                                    H H H                                                                              yellowish red yellowish                                                        red yellowish red             94 95 96                                                                             ##STR103##             SO.sub.3 H  SO.sub.3 H SO.sub.3 H                                                  H H CH.sub.3                                                                      H H H                                                                             CH.sub.3 OCH.sub.3 H                                                                 H H CH.sub.3                                                                       red red red                   97 98                                                                                ##STR104##             SO.sub.3 H SO.sub.3 H                                                              H H                                                                               H H                                                                               OCH.sub.3 CH.sub.3                                                                   H H orange orange                 __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________      ##STR105##                                                                    Ex.                                    Hue or                                  No. X.sup.1                                                                             R.sup.1                                                                             R.sup.2                                                                            R.sup.3                                                                             R.sup.5                                                                             R.sup.4                                                                             G     λ.sub.max  [nm]                  __________________________________________________________________________      99 H    H    H   CH.sub.3                                                                            H    H    CH.sub.3                                                                             421                                     100 H    H    H   C.sub.2 H.sub.5                                                                     H    H    CH.sub.3                                                                             421                                     101 H    H    CH.sub.3                                                                           CH.sub.3                                                                            H    H    CH.sub.3                                                                             422                                     102 H    CH.sub.3                                                                            H   CH.sub.3                                                                            H    H    CH.sub.3                                                                             420                                     103 H    OCH.sub.3                                                                           H   H    CH.sub.3                                                                            H    CH.sub.3                                                                             422                                     104 H    CH.sub.3                                                                            H   OCH.sub.3                                                                           H    H    C.sub.2 H.sub.5                                                                      423                                     105 H    H    H   CH.sub.3                                                                            H    Cl   CH.sub.3                                                                             421                                     106 H    H    H   C.sub.2 H.sub.5                                                                     H    Cl   CH.sub.3                                                                             421                                     107 H    H    H   OCH.sub.3                                                                           H    Cl   CH.sub.3                                                                             422                                     108 SO.sub.3 H                                                                          H    CH.sub.3                                                                           CH.sub.3                                                                            H    H    C.sub.2 H.sub.5                               109 SO.sub.3 H                                                                          CH.sub.3                                                                            H   CH.sub.3                                                                            H    H    C.sub.2 H.sub.5                               110 SO.sub.3 H                                                                          H    H   C.sub.2 H.sub.5                                                                     H    H    CH.sub.3                                      111 SO.sub.3 H                                                                          H    H   C.sub.2 H.sub.5                                                                     H    Cl   CH.sub.3                                      112 H    H    H   C.sub.2 H.sub.5                                                                     SO.sub.3 H                                                                          H    CH.sub.3                                                                             421                                     113 H    H    H   C.sub.2 H.sub.5                                                                     SO.sub.3 H                                                                          Cl   CH.sub.3                                                                             421                                     114 H    H    CH.sub.3                                                                           CH.sub.3                                                                            SO.sub.3 H                                                                          H    CH.sub.3                                                                             421                                     115 H    H    CH.sub.3                                                                           CH.sub.3                                                                            SO.sub.3 H                                                                          H    C.sub.4 H.sub.9 (n)                                                                  421                                     116 H    H    CH.sub.3                                                                           OCH.sub.3                                                                           H    Cl   CH.sub.3                                                                             422                                     117 SO.sub.3 H                                                                          H    CH.sub.3                                                                           CH.sub.3                                                                            H    OCH.sub.3                                                                           CH.sub.3                                      118 H    H    H   CH.sub.3                                                                            H    OCH.sub.3                                                                           CH.sub.3                                      __________________________________________________________________________

EXAMPLE 119 ##STR106## Brilliant greenish yellow on leather, nylon and wool. EXAMPLE 120 ##STR107## Bright greenish yellow on leather, nylon and wool. EXAMPLE 121 ##STR108## Greenish yellow on leather, nylon and wool. EXAMPLE 122 ##STR109## Greenish yellow on nylon, wool and leather. EXAMPLE 123 ##STR110## Greenish yellow on leather and wool. EXAMPLE 124 ##STR111## EXAMPLE 125 ##STR112## EXAMPLE 126 ##STR113## EXAMPLE 127 ##STR114## EXAMPLE 128 ##STR115## EXAMPLE 129 ##STR116## EXAMPLE 130 ##STR117## EXAMPLE 131 ##STR118## EXAMPLE 132 ##STR119##

                  TABLE 7                                                          ______________________________________                                         Example                                λ.sub.max  (H.sub.2 O)           No.    R.sup.1 R.sup.2   R.sup.3                                                                              Hue     [nm]                                    ______________________________________                                         133    H       CH.sub.3  H     bright red                                                                             509                                     134    H       C.sub.2 H.sub.5                                                                          H     bright red                                                                             509                                     135    H       CH(CH.sub.3).sub.2                                                                       H     bright red                                                                             508                                     136    CH.sub.3                                                                               CH.sub.3  H     bright red                                                                             509                                     137    CH.sub.3                                                                               H         CH.sub.3                                                                             bright red                                                                             509                                     138    H       CH.sub.3  CH.sub.3                                                                             bright red                                                                             509                                     139    H       C.sub.6 H.sub.5                                                                          H     bright red                                                                             512                                     140    H       Cl        H     bright red                                                                             511                                     141    H       CH.sub.3  Cl    bright red                                                                             510                                     ______________________________________                                    

EXAMPLE 142 (use)

100 parts by weight of a retanned chrome leather having a shaved thickness of 1.4 mm were neutralized by drumming for 45 minutes in 200 parts by weight of water at 30° C. with 1 part by weight of sodium bicarbonate and 1 part by weight of sodium formate. The leather was then washed in 200 parts by weight of fresh water at 30° C. by drumming for 15 minutes. Thereafter the dyeing was effected by drumming for 45 minutes in 200 parts by weight of water at 50° C. containing 1% by weight of the dye described in Example 2. Then 4 parts by weight of a commercial fat liquor were added and drumming was continued for 30 minutes. After acidification with 0.5 part by weight of formic acid, the leather was drummed for a further 30 minutes and then rinsed with cold water, set out, dried, sawdusted, staked and strained.

The result obtained was leather dyed in a deep bright yellow shade having good light fastness and good wet fastness properties.

Similar results are obtained in the dyeing of leather with the dyes listed hereinafter.

                                      TABLE 8                                      __________________________________________________________________________      ##STR120##                                                                    Example                                                                        No.  L.sup.1                                                                             X.sup.1                                                                            K                       Hue                                      __________________________________________________________________________     143  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR121##             greenish yellow                          144  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR122##             greenish yellow                          145  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR123##             greenish yellow                          146  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR124##             greenish yellow                          147  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR125##             greenish yellow                          148  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR126##             greenish yellow                          149  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR127##             greenish yellow                          150  CH.sub.2O                                                                           H                                                                                   ##STR128##             greenish yellow                          151  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR129##             bluish red λ.sub.max                                                    (H.sub.2 O): 529 nm                      152  CH.sub.2 CH.sub.2                                                                   H                                                                                   ##STR130##             orange                                   153  CH.sub.2 CH.sub.2                                                                   SO.sub.3 H                                                                          ##STR131##             greenish yellow                          154  CH.sub.2 CH.sub.2                                                                   SO.sub.3 H                                                                          ##STR132##             greenish yellow                          155  CH.sub.2 CH.sub.2                                                                   SO.sub.3 H                                                                          ##STR133##             greenish yellow                          __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________      ##STR134##                                                                    Example No.                                                                           R.sup.1                                                                            R.sup.2                                                                            R.sup.3                                                                            K                    Hue                                    __________________________________________________________________________     156    H   CH.sub.3                                                                           H                                                                                   ##STR135##          reddish orange                         157    H   CH.sub.3                                                                           H                                                                                   ##STR136##          reddish orange                         158    H   C.sub.2 H.sub.5                                                                    H                                                                                   ##STR137##          reddish orange                         159    H   CH.sub.3                                                                           CH.sub.3                                                                            ##STR138##          reddish orange                         160    CH.sub.3                                                                           CH.sub.3                                                                           H                                                                                   ##STR139##          orange                                 __________________________________________________________________________

EXAMPLE 161

42.1 g of the diazo component of the formula ##STR140## were stirred at room temperature with 90 ml of 25% strength by weight hydrochloric acid and 10 drops of a wetting agent effective under acid conditions. After 2 hours 100 g of ice were added and the suspension was admixed with a total of 64 ml of 23% strength by weight aqueous sodium nitrite solution while cooling was applied. The diazotization batch was subsequently stirred at from 0° to 8° C. for 2.5 hours. Excess nitrous acid was then completely destroyed with amidosulfuric acid and the diazonium salt solution obtained was diluted with 150 ml of ice-water. The mixture was then added to 65.1 g of the coupling component of the formula ##STR141## which had been dissolved at pH 7 in 300 ml of water and 300 ml of ice. During the addition of the diazonium salt solution the pH of the reaction mixture was maintained within the range from 4 to 7 by adding sodium hydroxide solution. The coupling did not take long. The honey yellow dye solution obtained was spray dried at a pH of from 4 to 6, giving 122 g of the dye of the formula ##STR142## in the form of the sodium salt of the sulfonic acids. The yellow powder still contains sodium chloride.

From 0.5 to 1% strength dyeings with this dye on retanned leather are a bright, very good wet-fast and light-last greenish yellow. λ_(max) (H₂ O): 421 nm.

Replacing the abovementioned diazo component by a compound of the formula: ##STR143## gives a yellow dye of the formula ##STR144## which has a similar fastness profile.

The same method gives the following compounds and the dyes listed below in Tables 11 and 12.

EXAMPLE 162 ##STR145## EXAMPLE 163 ##STR146##

                                      TABLE 10                                     __________________________________________________________________________     Ex. No.                                                                             Q.sup.1           Z.sup.o                                                                           a λ.sub.max  [nm] (in water)                                                        Hue                                      __________________________________________________________________________     164                                                                                  ##STR147##       H  1 431       yellow                                   165                                                                                  ##STR148##       H  1 431       yellow                                   166                                                                                  ##STR149##       H  1           yellow                                   167                                                                                  ##STR150##       H  1 431       yellow                                   168                                                                                  ##STR151##       H  1           yellow                                   169                                                                                  ##STR152##       H  1           yellow                                   170  C.sub.6 H.sub.5   H  1           greenish yellow                          171                                                                                  ##STR153##       H  1 431       greenish yellow                          172                                                                                  ##STR154##       H  1 432       greenish yellow                          173                                                                                  ##STR155##       H  1 432       greenish yellow                          174                                                                                  ##STR156##       H  1 429       greenish yellow                          175                                                                                  ##STR157##       H  0 430       greehish yellow                          176                                                                                  ##STR158##       CH.sub.3                                                                          1 431       greenish yellow                          177                                                                                  ##STR159##       CH.sub.3                                                                          2 431       greenish yellow                          178                                                                                  ##STR160##       H  0 430       greenish yellow                          179                                                                                  ##STR161##       H  1 430       greenish yellow                          180                                                                                  ##STR162##       CH.sub.3                                                                          1 431       greenish yellow                          181                                                                                  ##STR163##       H  1 431       greenish yellow                          182                                                                                  ##STR164##       H  1 430       greenish yellow                          183                                                                                  ##STR165##       H  1 430       greenish yellow                          184                                                                                  ##STR166##       H  1 429       greenish yellow                          185                                                                                  ##STR167##       H  1 430       greenish yellow                          186                                                                                  ##STR168##       H  1 430       greenish yellow                          187                                                                                  ##STR169##       H  1 432       yellow                                   188                                                                                  ##STR170##       H  1 432       yellow                                   189                                                                                  ##STR171##       H  1 432       yellow                                   190                                                                                  ##STR172##       H  1 431       greenish yellow                          191                                                                                  ##STR173##       CH.sub.3                                                                          1 431       greenish yellow                          __________________________________________________________________________

                                      TABLE 11                                     __________________________________________________________________________      ##STR174##                                                                    Ex. No.                                                                             Q.sup.2                    λ.sub.max  [nm] (in                                                               Hueer)                               __________________________________________________________________________     192                                                                                  ##STR175##                          bluish red                           193                                                                                  ##STR176##                          bluish red                           194                                                                                  ##STR177##                513       bluish red                           195                                                                                  ##STR178##                513       bluish red                           196                                                                                  ##STR179##                513       bluish red                           197                                                                                  ##STR180##                513       bluish red                           198                                                                                  ##STR181##                513       bluish red                           199                                                                                  ##STR182##                513       bluish red                           __________________________________________________________________________

                  TABLE 12                                                         ______________________________________                                          ##STR183##                                                                    Ex. No. Q.sup.1         Q.sup.3                                                                               Hue                                             ______________________________________                                         200                                                                                     ##STR184##     CH.sub.2                                                                              greenish yellow                                 201                                                                                     ##STR185##     C.sub.2 H.sub.4                                                                       greenish yellow                                 202                                                                                     ##STR186##     CH.sub.2                                                                              greenish yellow                                 203                                                                                     ##STR187##     C.sub.2 H.sub.4                                                                       greenish yellow                                 ______________________________________                                    

EXAMPLE 204

257 g of 1-(2-phenylethyl)-6-hydroxy-3-cyano-4-methypyrid-2-one were introduced at not more than 70° C. into a mixture of 160 g of 100% strength by weight sulfuric acid and 380 g of oleum (24% strength by weight). The resulting solution was subsequently stirred at 75° C. for 5 hours to form essentially a product of the formula ##STR188## This was followed by heating over 5 hours to 110° C. to hydrolyze the cyano group and decarboxylate the carboxylic acid intermediate (foaming due to CO₂ evolution). Then the mixture was heated to 130°-135° C. and stirred at that temperature for 5.5 hours. After the reaction mixture had been cooled down to about 110° C., it was stirred into about 900 g of ice-water and the compound of the formula ##STR189## was neutralized at ≦30° C. with sodium hydroxide solution. This solution can be used directly for preparing azo dyes. λ_(max) (H₂ O): 325 nm, 247 nm (minimum at 280 and 235 nm).

                                      TABLE 13                                     __________________________________________________________________________     Example No.                                                                           Q.sup.1           Z.sup.o                                                                           a λ.sub.max  [nm] (in                                                               Hueer)                                 __________________________________________________________________________     205    C.sub.6 H.sub.5   H  1           greenish yellow                        206                                                                                    ##STR190##       H  1 431       greenish yellow                        207                                                                                    ##STR191##       H  1 432       greenish yellow                        208                                                                                    ##STR192##       H  1 432       greenish yellow                        209                                                                                    ##STR193##       H  1 429       greenish yellow                        210                                                                                    ##STR194##       H  0 430       greenish yellow                        211                                                                                    ##STR195##       CH.sub.3                                                                          1 431       greenish yellow                        212                                                                                    ##STR196##       CH.sub.3                                                                          2 431       greenish yellow                        213                                                                                    ##STR197##       H  0 430       greenish yellow                        214                                                                                    ##STR198##       H  1 430       greenish yellow                        215                                                                                    ##STR199##       CH.sub.3                                                                          1 431       greenish yellow                        216                                                                                    ##STR200##       H  1 431       greenish yellow                        217                                                                                    ##STR201##       H  1 430       greenish yellow                        218                                                                                    ##STR202##       H  1 430       greenish yellow                        219                                                                                    ##STR203##       H  1 429       greenish yellow                        220                                                                                    ##STR204##       H  1 430       greenish yellow                        221                                                                                    ##STR205##       H  1 430       greenish yellow                        222                                                                                    ##STR206##       H  1 432       yellow                                 223                                                                                    ##STR207##       H  1 432       yellow                                 224                                                                                    ##STR208##       H  1 432       yellow                                 225                                                                                    ##STR209##       H  1 431       greenish yellow                        226                                                                                    ##STR210##       CH.sub.3                                                                          1 431       greenish yellow                        __________________________________________________________________________

                                      TABLE 14                                     __________________________________________________________________________      ##STR211##                                                                    Example No.                                                                           Q.sup.2                    λ.sub.max  [nm] (in                                                               Hueer)                             __________________________________________________________________________     227                                                                                    ##STR212##                          bluish red                         228                                                                                    ##STR213##                          bluish red                         229                                                                                    ##STR214##                513       bluish red                         230                                                                                    ##STR215##                513       bluish red                         231                                                                                    ##STR216##                513       bluish red                         232                                                                                    ##STR217##                513       bluish red                         233                                                                                    ##STR218##                513       bluish red                         234                                                                                    ##STR219##                513       bluish red                         __________________________________________________________________________

                  TABLE 15                                                         ______________________________________                                          ##STR220##                                                                    Example No.                                                                              Q.sup.1       Q.sup.3  Hue                                           ______________________________________                                         235                                                                                       ##STR221##   CH.sub.2 greenish yellow                               236                                                                                       ##STR222##   C.sub.2 H.sub.4                                                                         greenish yellow                               237                                                                                       ##STR223##   CH.sub.2 greenish yellow                               238                                                                                       ##STR224##   C.sub.2 H.sub.4                                                                         greenish yellow                               ______________________________________                                    

EXAMPLE 239

257 g of 1-(2-phenylethyl)-6-hydroxy-3-cyano-4-methylpyrid-2-one were added at not more than 70° C. to a mixture of 160 g of 100% by weight sulfuric acid and 380 g of 24% by weight oleum. The solution formed was subsequently stirred at 75° C. for 5 hours, producing essentially a product of the formula ##STR225## This was followed by heating at 110° C. for 5 hours, during which the cyano group hydrolyzed and the carboxylic acid intermediate was decarboxylated (foaming due to CO₂ evolution ). Then the reaction mixture was heated to 130°-135° C. and stirred at that temperature for 5.5 hours. After the reaction mixture had cooled down to about 110° C., it was stirred out onto about 900 g of ice-water, and the compound of the formula ##STR226## was neutralized at ≦30° C. with sodium hydroxide solution. This solution can be used directly for preparing azo dyes. λ_(max) (H₂ O): 325 run, 247 run, (minimum at 280 and 235 nm). 

We claim:
 1. A pyridone compound of the formula II ##STR227## where n is 1 or 2,Z^(o) is hydrogen or C₁ -C₄ -alkyl, and Z¹ is hydrogen, C₁ -C₄ -alkyl or phenyl.
 2. A process for preparing a pyridone compound of the formula IIa ##STR228## where a is 0, 1 or 2,Z^(o) is hydrogen or C₁ -C₄ -alkyl, and Z¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, by reacting a pyridone of the formula IIb ##STR229## where W⁴ is cyano or acetyl and a, Z^(o) and Z¹ are each as defined above, with oleum, wherein said oleum contains from 1 to 2 mol of free sulfur trioxide and said reaction comprising a first stage at from 0° to 75° C. for from 1 to 5 hours and then a second stage at from 80° to 135° C. for from 2 to 11 hours. 